US7763233B2 - Hydrogen generator and fuel cell using same - Google Patents

Hydrogen generator and fuel cell using same Download PDF

Info

Publication number
US7763233B2
US7763233B2 US12/109,595 US10959508A US7763233B2 US 7763233 B2 US7763233 B2 US 7763233B2 US 10959508 A US10959508 A US 10959508A US 7763233 B2 US7763233 B2 US 7763233B2
Authority
US
United States
Prior art keywords
hydride
hydrogen
water
conduit
generating device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US12/109,595
Other languages
English (en)
Other versions
US20090017346A1 (en
Inventor
Jean-Yves Laurent
Frédéric Gaillard
Philippe Capron
Denis Locatelli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique CEA filed Critical Commissariat a lEnergie Atomique CEA
Assigned to COMMISSARIAT A L'ENERGIE ATOMIQUE reassignment COMMISSARIAT A L'ENERGIE ATOMIQUE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CAPRON, PHILIPPE, GAILLARD, FREDERIC, LAURENT, JEAN-YVES, LOCATELLI, DENIS
Publication of US20090017346A1 publication Critical patent/US20090017346A1/en
Application granted granted Critical
Publication of US7763233B2 publication Critical patent/US7763233B2/en
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/065—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of inorganic compounds with hydrides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to the preparation of hydrogen generating devices, in particular for generating hydrogen gas. In a manner known per se, this production can be achieved by the hydrolysis of a borohydride.
  • This invention has an application in particular as a generator for fuel cells of the Proton Exchange Membrane Fuel Cells (PEMFC) type. More particularly, in the context of this application, the present invention relates to fuel cells for supplying electricity to portable electric or electronic devices, that is, devices requiring low electric power. However, this invention can find applications for supplying hydrogen to higher capacity fuel cells.
  • PEMFC Proton Exchange Membrane Fuel Cells
  • Fuel cells represent a non-polluting and alternative energy source to hydrocarbon combustion, particularly for motor vehicles.
  • a fuel cell is a battery in which the electricity is generated by the oxidation of a reducing fuel, for example hydrogen, on an electrode, coupled with the reduction of an oxidizer, such as oxygen in the air, on the other electrode.
  • the hydrogen oxidation reaction can be accelerated by using a catalyst which generally contains a metallic element.
  • One of the known methods for producing hydrogen is to hydrolyze borohydrides in solid form, like sodium borohydride or tetrahydroborate NaBH 4 , dissolved and contacted with a solid catalyst material.
  • the sodium borohydride is hydrolyzed under certain conditions by the following reaction: M(BH 4 ) n +2nH 2 O ⁇ M[B(OH) 4 ] n +4nH 2
  • M is an alkali or alkaline earth element and n is a positive whole number equal to the number of valency electrons of the element M.
  • the element M may for example be sodium (Na), in which case the number n is 1, giving rise to the following reaction: NaBH 4 +2H 2 O ⁇ NaB(OH) 4 +4H 2 .
  • the element M may be potassium (K), lithium (Li) or another appropriate element.
  • This borohydride hydrolysis reaction has the advantage of involving reagents and residues which are harmless, that is, non-toxic and non-polluting, as opposed for example to the reactions occurring in the Direct Methanol Fuel Cell (DMFC) or Formic Acid Fuel Cell (FAFC) fuel cells, which use methanol and formic acid respectively as fuel.
  • DMFC Direct Methanol Fuel Cell
  • FAFC Formic Acid Fuel Cell
  • the commonly used sodium borohydride generates four moles of hydrogen by reacting with two moles of water.
  • some prior art reactors use borohydrides in solid form, for example in the divided state, that is in powder form.
  • the hydrogen is then generated by contacting the solid borohydride with an aqueous solution preferably containing a catalyst material.
  • reaction by-products frequently obstruct the water intake line in the reactor containing the solid borohydride.
  • reaction kinetics is liable to fluctuate according to the extent of this obstruction of the water intake.
  • the object of the present invention is to provide a hydrogen generator that does not have the drawbacks of the prior art.
  • the subject of the present invention is therefore a device for generating hydrogen by hydrolysis of a hydride, allowing better control of the reaction kinetics, and hence the flow of hydrogen generated, while avoiding the risks of obstruction of the water intake.
  • the present invention thus relates to a device for generating hydrogen by hydrolysis of a hydride comprising:
  • the envelope is suitable for contacting the water with the hydride in a site capable of serving as the seat of the hydrolysis reaction and of moving in the reactor as the material constituting the envelope is consumed by the hydrolysis reaction products.
  • envelope means one (or more) material(s) surrounding and covering one of the reagents. This definition therefore pertains directly to the common meaning of the term “envelope.”
  • the reactor further comprises at least one orifice that coincides with a line formed by the envelope to convey the water into the reactor.
  • the water intake line is inserted into the reactor and is dissolved by the hydrolysis reaction products as the hydride is consumed; this pipe is therefore shortened as this reaction advances.
  • the reactor contains the quantity of water necessary to hydrolyze all the hydride that it contains.
  • This water is separated from the hydride by the envelope made from a consumable material.
  • this envelope does not contain the water but the hydride, and moreover, before any use of the device, it is mainly covered with a lining made from a material that is dispersible but not soluble in the water.
  • the lining impermeabilizes the immersed envelope and protects it from premature dissolution.
  • this envelope may have the shape of a cylinder or a cone, having a circular or polygonal base.
  • Such shapes are suitable for forming a water intake at controlled flow rate and for predicting the consumption time of the envelope having such a predefined shape. These shapes therefore serve to accurately control the hydrogen flow.
  • the hydrogen generator has a plurality of envelopes, having a similar or dissimilar geometry, and distributed in the reactor. This serves to even further improve the control of the hydrolysis reaction by increasing the number of water inlets at controlled flow rate in the reactor.
  • the hydride is selected from the group comprising sodium tetrahydroborate (NaBH 4 ), magnesium tetrahydroborate (Mg(BH 4 ) 2 ) and lithium hydride (LiH). These three compounds produce non-polluting reaction residues. They have a high hydrogen generating capacity. Sodium tetrahydroborate NaBH 4 is also the most advantageous, because it is easy to produce and inexpensive.
  • the hydride may also be selected from the group comprising LiBH 4 , Al(BH 4 ) 3 , Be(BH 4 ) 2 , MgH 2 , CaH 2 , Ca(AlH 4 ) 2 , Zr(BH 4 ) 3 , Ca(BH 4 ) 2 , NaAlH 4 , KBH 4 , LiAlH 4 .
  • the consumable material constituting the envelope of the invention may be made from a metallic material that corrodes or an organic material that is degraded in the presence of a basic medium.
  • this material is consumed due to the concomitant generation of hydroxide ions.
  • This organic material may be selected from polyamides, polycarbonates, PET (polyethylene terephthalate), polyesters, PVDF (polyvinylidene fluoride), PBT (polybutyl terephthalate).
  • this material may be a material whereof the dissolution under the action of the reaction products also produces hydrogen.
  • This second hydrogen production reaction increases the total quantity of hydrogen produced in the reactor, thereby serving to improve the ratio of hydrogen produced to the weight of the generator.
  • this material may be aluminium or an aluminium alloy.
  • Aluminum is in fact corroded by the hydroxide ions produced by the hydrolysis reaction, thereby producing hydrogen and alumina by the following reaction: 2Al+6OH ⁇ ⁇ Al 2 O 3 +3H 2
  • this reaction has the advantage of lowering the pH by consuming hydroxide ions, which would slow down the main hydride hydrolysis reaction.
  • a catalyst is introduced into the reactor in the form of a salt dissolved in the water or in the form of solid particles distributed in the hydride.
  • This catalyst serves to increase the yield of the reaction, and its direct addition in one of the reagents present avoids its specific introduction into the reactor, thereby simplifying the use of the generator.
  • the element constituting this catalyst may be selected from the group comprising ruthenium (Ru), platinum (Pt), cobalt (Co), palladium (Pd), nickel (Ni), iron (Fe), gold (Au), silver (Ag), manganese (Mn), rhenium (Re), rhodium (Rh), titanium (Ti), vanadium (V) and cerium (Ce). If one or more of these metals is used to form the catalyst particles, it is possible to reach good reaction yields for generating hydrogen by the hydrolysis of a hydride.
  • the quantities of hydride and water in the reactor are selected and the envelope characteristic of the invention is dimensioned in order to produce a predefined hydrogen flow rate.
  • the present invention also relates to a fuel cell comprising an electrolyte, an anode and a cathode, whereof the oxidizer is oxygen (O 2 ), and the reducing agent is hydrogen (H 2 ) produced by hydrolysis.
  • the invention comprises a device for generating hydrogen by hydrolysis of a hydride, as previously described.
  • FIG. 1 is a schematic representation of a system comprising a fuel cell for powering a portable electronic device.
  • FIGS. 2 a , 2 b and 2 c are schematic representations of various states of a device according to a first embodiment of the invention.
  • FIG. 3 is a schematic representation of a device according to a second embodiment of the invention.
  • FIG. 1 therefore illustrates a schematic representation of a system comprising a fuel cell 1 —subject matter of the invention—for powering a portable electronic device, in this case a mobile telephone 2 .
  • the power supply is provided via a battery 3 called buffer battery, suitable for stabilizing the electric current delivered to the mobile telephone 2 .
  • the fuel cell 1 conventionally comprises an electrolyte, an anode and a cathode. It uses oxygen gas (O 2 ) as oxidizer and, as reducing agent, hydrogen gas (H 2 ) produced using a generator 5 according to the present invention.
  • the cell thus described may in particular supply power to low power devices, that is, typically requiring between 1 W and 100 W.
  • the generator 5 comprises a fuel reserve 4 ′ which is connected, via a quick coupling having two matching parts 6 and 7 , in an appropriate housing 4 provided in the cell 1 .
  • FIGS. 2 a to 2 c illustrate a first embodiment of the invention.
  • the generator comprises a reactor 28 , whereof the body houses the seat of the hydrogen production reaction.
  • This body of the reactor 28 has an orifice 27 for allowing the removal of the hydrogen gas produced.
  • a line for transporting the hydrogen to the fuel cell 1 can be mounted on this orifice 27 .
  • the body of the reactor 28 contains sodium borohydride 22 in solid form in the state of an aggregate powder.
  • the sodium borohydride NaBH 4 occupies most of the volume of the reactor body 28 , here, leaving unobstructed the orifice 27 for removing the hydrogen produced by the hydrolysis reaction.
  • borohydride of another alkali or alkaline earth element such as magnesium (Mg) (formula Mg(BH 4 ) 2 ).
  • Mg magnesium
  • borohydrides serve to obtain a high yield for the hydrogen generation reaction.
  • the use of these borohydrides does not demand any particular safety measures, because they are harmless, that is, they are non-polluting and non-toxic.
  • a catalyst is introduced into the reactor 28 in the form of a salt dissolved in the water of the reaction. It is also possible to introduce the catalyst in the form of solid particles distributed in the hydride 22 . The addition of catalysts directly to one of the reagents present avoids the separate introduction thereof into the reactor, automatically simplifying the use of the generator.
  • This catalyst may be selected from the group comprising ruthenium (Ru), platinum (Pt), cobalt (Co), palladium (Pd), nickel (Ni), iron (Fe), gold (Au), silver (Ag), manganese (Mn), rhenium (Re), rhodium (Rh), titanium (Ti), vanadium (V) and cerium (Ce).
  • the device according to the invention comprises means for releasing the water 24 required for the hydrolysis reaction, the means serving to convey the water 24 into the reactor 28 .
  • the means consist of a line 21 for water intake 24 controlled by a valve not shown. This line 21 terminates, via an orifice 29 made in a wall of the reactor 28 , in a line 23 , of which one of the functions is to convey the water 24 to the seat of the hydrolysis reaction.
  • This line 23 is formed by a cylindrical envelope having a circular base.
  • This cylindrical envelope serves to isolate the water 24 conveyed from the hydride 22 contained in the reactor 28 , except at the seat provided for the hydrolysis reaction.
  • the envelope or line 23 surrounds, covers and “protects” one of the reagents, in this case the water 24 .
  • the line 23 therefore has a hollow shape for containing and surrounding the hydride 22 .
  • the envelope forming the line 23 is made from aluminium.
  • This metal is known to corrode in basic medium, which is the specific medium obtained by the hydride hydrolysis reaction. This is because the hydrolysis reaction produces hydroxide ion (OH ⁇ ). Thus the pH resulting from the hydrolysis reaction may reach a value of about 11.
  • this hydrogen production “side” reaction increases the total quantity of hydrogen produced in the reactor and commensurately improves the ratio of the hydrogen produced to the weight of the generator, a sort of “mass efficiency” of the reaction.
  • this reaction has the advantage of lowering the pH in the seat of the reaction by consuming the hydroxide ions, which would slow down the main hydride hydrolysis reaction.
  • This consumption of hydroxide ions in the corrosion of the aluminium thus avoids the fluctuations in the production of hydrogen due to the lowering of the pH.
  • this corrosion of the aluminium has the result of progressively consuming the envelope forming the line 23 .
  • this envelope releases the water 24 required for the hydrolysis, locally and progressively.
  • this release of water 24 is “localized” because it only occurs at the end of 26 of the line 23 , whereof the position in the reactor varies with the aluminium consumption previously described.
  • the adjective “localized” designates a relatively restricted reaction exchange area, with regard in particular to the length of the envelope 23 .
  • the location of the release of the water 24 varies within the reactor 28 , but due to the consumption of the line, the release of the water 24 is always located in the zone where the hydrolysis reaction occurs, that is, as the hydride consumption proceeds.
  • the line 23 cannot be obstructed by the products 25 issuing from the hydrolysis reaction, which sometimes have a compact consistency.
  • this release of water 24 is progressive because it results from the progressive consumption of the envelope by the hydrolysis reaction products.
  • the envelope is thus consumed as the production of hydroxide ions by the hydrolysis reaction advances.
  • its end 26 moves progressively with the seat of the reaction towards zones where the hydride 22 has not yet been hydrolyzed.
  • the envelope 23 is dimensioned to make its own consumption by corrosion match the hydrolysis of the hydride. As an example, a period of about 3 hours can be predicted for corroding half of the 50 ⁇ m thick walls of an aluminium tube.
  • FIG. 3 shows an alternative embodiment of the invention, in which the water is no longer conveyed from outside the reactor 38 , but is directly contained in the reactor 38 .
  • the water is isolated from the hydride 32 by an envelope 33 , except locally at the seat provided for the initiation of the hydrolysis reaction.
  • the hydride 32 is contained here in this envelope 33 , contrary to the embodiment shown in FIGS. 2 a to 2 c.
  • the isolating envelope is made from aluminium. It corrodes progressively and locally, similar to the aluminium forming the line 23 as the hydrolysis reaction proceeds.
  • this line 33 has the form of a coil, in order to localize the seat of the hydrolysis reaction more effectively, as the reaction proceeds.
  • the corrosion reaction of the aluminium forming the coil has the same characteristics and advantages as those described in connection with the preceding embodiment.
  • a lining 39 is deposited on most of the aluminium envelope 33 .
  • This lining 39 consists of a layer of a material that is inert to water.
  • inert means a material that does not react and remains unchanged in contact with the water; the lining is therefore insoluble in the water.
  • This lining 39 thereby “protects” the envelope 33 from corrosion in the areas where it is deposited, by making it impervious.
  • the envelope 33 corrodes locally and only at the end 36 where it is not covered by the lining 39 and where it does not cover the hydride 32 .
  • the immersed envelope 33 is therefore “protected” against premature dissolution, that is, more rapid than anticipated.
  • the envelope 33 is therefore mostly covered by the lining 39 and the overall combination is immersed in the water.
  • the envelope 33 comes into contact with the water 34 , here at its end 36 , the hydrolysis reaction takes place as previously described.
  • the water is introduced entirely, thereby triggering the start of the hydrolysis reaction.
  • the lining 39 is formed of a sufficiently fine layer to make it dispersible in the water 34 in the absence of the solid support provided by the envelope 33 .
  • the lining 39 losses its support and hence is dispersed in the water in small particles. These particles are not dissolved, because the material constituting the lining 39 is insoluble in water, as stated above.
  • the thickness of the lining 39 therefore represents a compromise between the function of impermeabilizing the envelope 33 and the necessary dispersion of the lining 39 in the liquid contained in the reactor 38 .
  • the water 34 comes into contact with the hydride locally and progressively, the progression resulting from the consumption of the material constituting the envelope 33 by the hydrolysis reaction products.
  • the envelope 33 here has the shape of a cylinder with a circular base, whereof the generating line is curved, in order to form a sort of “coil”, thereby increasing the compactness of the device.
  • the envelopes forming the line 23 or the coil 33 have the shape of a cylinder with a circular base, but they could also be conical and/or have a polygonal cross section.
  • the device may comprise a plurality thereof, having similar or dissimilar geometries and distributed in the reactor. This serves to further improve the control of the reaction by increasing the number of controllable water intakes in the reactor. Similarly, a plurality of “coils” can be immersed in the reactor 38 .
  • the choice of their number, geometries and positions in a particular reactor depends on the advancement of the desired hydrolysis reaction, as a function of the total hydrogen production time provided for this generator. Similarly, it is advantageous to select the quantities of hydride 22 , 32 and water 24 , 34 placed in the reactor 28 , 38 , in order to produce the predefined hydrogen flow rate during a desired period.
  • hydride coils that are elongated and have an orthogonal cross section and a constant surface area.
  • the form of the hydride in its envelope serves as a support for the movement of the seat of the hydrolysis reaction. This is why this form is advantageously elongated, in order to obtain a progressive hydrolysis of the hydride.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Fuel Cell (AREA)
  • Hydrogen, Water And Hydrids (AREA)
US12/109,595 2005-11-24 2008-04-25 Hydrogen generator and fuel cell using same Expired - Fee Related US7763233B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR05.53587 2005-11-24
FR0553587A FR2893606B1 (fr) 2005-11-24 2005-11-24 Generateur d'hydrogene et pile a combustible mettant en oeuvre un tel generateur
FR0553587 2005-11-24
PCT/FR2006/051221 WO2007060369A1 (fr) 2005-11-24 2006-11-23 Générateur d'hydrogène et pile à combustible mettant en oeuvre un tel générateur

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2006/051221 Continuation WO2007060369A1 (fr) 2005-11-24 2006-11-23 Générateur d'hydrogène et pile à combustible mettant en oeuvre un tel générateur

Publications (2)

Publication Number Publication Date
US20090017346A1 US20090017346A1 (en) 2009-01-15
US7763233B2 true US7763233B2 (en) 2010-07-27

Family

ID=37027737

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/109,595 Expired - Fee Related US7763233B2 (en) 2005-11-24 2008-04-25 Hydrogen generator and fuel cell using same

Country Status (9)

Country Link
US (1) US7763233B2 (de)
EP (1) EP1954385B1 (de)
JP (1) JP5107254B2 (de)
CN (1) CN101312779B (de)
AT (1) ATE471205T1 (de)
DE (1) DE602006014991D1 (de)
ES (1) ES2343751T3 (de)
FR (1) FR2893606B1 (de)
WO (1) WO2007060369A1 (de)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2918583B1 (fr) * 2007-07-13 2011-06-10 Commissariat Energie Atomique Dispositif generateur de gaz portable et alimentation electrique a pile a combustible comportant un tel dispositif
FR2931812B1 (fr) * 2008-06-02 2010-05-14 Alex Hr Roustaei Batteries, micro piles jetables, rechargeables ou recyclables utilisant un systeme de pile a hydrogene nanotique
US20110236729A1 (en) * 2008-12-05 2011-09-29 Roustaei Alex Hr Hydrogen cells or microcells with a hydrogen generator
CN102130348A (zh) * 2010-01-15 2011-07-20 扬光绿能股份有限公司 燃料匣及储氢方法
CN102130347B (zh) * 2010-01-15 2013-10-16 扬光绿能股份有限公司 燃料电池的燃料匣与燃料匣操作方法
CN102142569A (zh) * 2010-01-29 2011-08-03 扬光绿能股份有限公司 氢气产生装置及具有其之燃料电池
WO2013015858A1 (en) 2011-07-26 2013-01-31 Eveready Battery Company, Inc. Hydrogen generator with improved fluid distribution
RU2510362C2 (ru) * 2012-04-23 2014-03-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" Способ получения высокочистого водорода
WO2013183798A1 (ko) * 2012-06-05 2013-12-12 Ryu Na Hyeon 보론 화합물을 포함하는 촉매 화합물 및 이를 이용한 물 분해 방법과 원유의 정제 방법
US10060577B2 (en) * 2013-10-28 2018-08-28 Alternative Fuel Containers, Llc Fuel gas storage tank with supporting filter tube(s)
EP3623808A1 (de) * 2018-09-17 2020-03-18 Seitz, Peter Elektrochemischer sensor zur messung des wassergehalts
FR3099854B1 (fr) * 2019-08-07 2021-10-22 Commissariat Energie Atomique Générateur de dihydrogène réutilisable
CN112234235A (zh) * 2020-10-06 2021-01-15 鄂尔多斯市国科能源有限公司 氢气发生装置及燃料电池系统
WO2023128748A1 (en) * 2021-12-27 2023-07-06 Nanomalaysia Berhad Hydrogen hybrid electric vehicle

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261955A (en) 1978-09-01 1981-04-14 The United States Of America As Represented By The Secretary Of The Army Vertical type porous membrane hydrogen generator
US4261956A (en) 1979-06-13 1981-04-14 Engelhard Minerals & Chemicals Corporation Cartridge for gas generator
US4373341A (en) * 1980-12-18 1983-02-15 Mahaffy & Harder Engineering Co. Expandible package for dispensing containers
US20010045364A1 (en) 2000-03-30 2001-11-29 Hockaday Robert G. Portable chemical hydrogen hydride system
WO2002030810A1 (de) 2000-10-12 2002-04-18 Manhattan Scientifics, Inc. Wasserstoffquelle zum betrieb einer brennstoffzelle, und hiermit bestückte brennstoffzelle
US20020182459A1 (en) 2001-06-01 2002-12-05 Hockaday Robert G. Fuel generator with diffusion ampoules for fuel cells
US20040035054A1 (en) * 2002-08-20 2004-02-26 Mohring Richard M. System for hydrogen generation
WO2005005311A2 (en) 2003-05-14 2005-01-20 Lynntech, Inc. Hydrogen generator
WO2005102914A2 (en) 2004-04-14 2005-11-03 Millennium, Cell, Inc. Systems and methods for hydrogen generation from solid hydrides

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54127891A (en) * 1978-03-29 1979-10-04 Fuji Electric Co Ltd Hydrogen generator
KR0124985B1 (ko) * 1994-08-17 1997-12-15 심상철 알칼리형 연료 전지
US20030008193A1 (en) * 2001-06-28 2003-01-09 Foamex L.P. Liquid fuel delivery system for fuel cells
US6924054B2 (en) * 2001-10-29 2005-08-02 Hewlett-Packard Development Company L.P. Fuel supply for a fuel cell
JP4201250B2 (ja) * 2002-11-12 2008-12-24 矢崎総業株式会社 水素生成装置
US7105033B2 (en) * 2003-02-05 2006-09-12 Millennium Cell, Inc. Hydrogen gas generation system
CN1438169B (zh) * 2003-03-27 2010-05-12 武汉大学 一种氢气的制备方法及装置
TWI381572B (zh) * 2003-11-14 2013-01-01 Encite Lllc 自動調節之氣體產生器和方法
JP4768966B2 (ja) * 2004-04-27 2011-09-07 東京瓦斯株式会社 発電装置

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261955A (en) 1978-09-01 1981-04-14 The United States Of America As Represented By The Secretary Of The Army Vertical type porous membrane hydrogen generator
US4261956A (en) 1979-06-13 1981-04-14 Engelhard Minerals & Chemicals Corporation Cartridge for gas generator
US4373341A (en) * 1980-12-18 1983-02-15 Mahaffy & Harder Engineering Co. Expandible package for dispensing containers
US20010045364A1 (en) 2000-03-30 2001-11-29 Hockaday Robert G. Portable chemical hydrogen hydride system
WO2002030810A1 (de) 2000-10-12 2002-04-18 Manhattan Scientifics, Inc. Wasserstoffquelle zum betrieb einer brennstoffzelle, und hiermit bestückte brennstoffzelle
US20020182459A1 (en) 2001-06-01 2002-12-05 Hockaday Robert G. Fuel generator with diffusion ampoules for fuel cells
US20040035054A1 (en) * 2002-08-20 2004-02-26 Mohring Richard M. System for hydrogen generation
WO2005005311A2 (en) 2003-05-14 2005-01-20 Lynntech, Inc. Hydrogen generator
WO2005102914A2 (en) 2004-04-14 2005-11-03 Millennium, Cell, Inc. Systems and methods for hydrogen generation from solid hydrides

Also Published As

Publication number Publication date
FR2893606B1 (fr) 2008-04-25
JP5107254B2 (ja) 2012-12-26
FR2893606A1 (fr) 2007-05-25
DE602006014991D1 (de) 2010-07-29
EP1954385B1 (de) 2010-06-16
ES2343751T3 (es) 2010-08-09
CN101312779B (zh) 2010-06-02
WO2007060369A1 (fr) 2007-05-31
EP1954385A1 (de) 2008-08-13
CN101312779A (zh) 2008-11-26
US20090017346A1 (en) 2009-01-15
JP2009517311A (ja) 2009-04-30
ATE471205T1 (de) 2010-07-15

Similar Documents

Publication Publication Date Title
US7763233B2 (en) Hydrogen generator and fuel cell using same
Kojima et al. Development of 10 kW-scale hydrogen generator using chemical hydride
TW522602B (en) Catalytic hydrogen storage composite material and fuel cell employing same
US9139432B1 (en) Apparatus for decomposing water and releasing hydrogen
JP5543270B2 (ja) アルコール改質のための金属支持銅触媒の使用
EP1891184B1 (de) Brennstoffe für kartuschen zur wasserstofferzeugung
US6930068B2 (en) Methanol reforming catalyst
CN101283075B (zh) 燃料电池盒中产生氢效率的优化
JP2006056753A (ja) 水素発生方法、水素発生装置及び燃料電池システム
US20080268310A1 (en) Hydrogen generating apparatus and fuel cell system using the same
JP2006298670A (ja) 水素発生方法及びその装置、並びに電気化学エネルギー生成方法及びそのシステム
CN101276928B (zh) 间接式硼氢化钠-肼混合燃料电池
US20080318104A1 (en) Electrolyte solution for hydrogen generating apparatus and hydrogen generating apparatus comprising the same
US20100159348A1 (en) Electro-catalytic recharging composition
US20110236729A1 (en) Hydrogen cells or microcells with a hydrogen generator
US7776776B2 (en) Method for preparing catalyst platinum supported on lithium cobalt oxide
KR20110002119A (ko) 지능형촉매수소발생시스템.
JP2002050375A (ja) 液体型燃料電池
JP2007317496A (ja) 燃料電池発電システム
JP2001342001A (ja) 水素発生触媒並びにそれを用いた水素発生方法及び装置
KR20180007112A (ko) 수중운동체의 수소공급시스템
JP2004342435A (ja) 燃料電池
JP2005103515A (ja) メタノール改質触媒及びその製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: COMMISSARIAT A L'ENERGIE ATOMIQUE, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LAURENT, JEAN-YVES;GAILLARD, FREDERIC;CAPRON, PHILIPPE;AND OTHERS;REEL/FRAME:020856/0451

Effective date: 20080303

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552)

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20220727